CN112955254B - Process for preparing double metal cyanide catalysts - Google Patents

Process for preparing double metal cyanide catalysts Download PDF

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CN112955254B
CN112955254B CN201980052752.3A CN201980052752A CN112955254B CN 112955254 B CN112955254 B CN 112955254B CN 201980052752 A CN201980052752 A CN 201980052752A CN 112955254 B CN112955254 B CN 112955254B
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dmc
metal cyanide
dispersion
polyether
molecular weight
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CN112955254A (en
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J·豪夫曼
M-T·格莱克斯纳
T·阿斯马
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Covestro Deutschland AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/11—Complex cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00539—Pressure

Abstract

The invention relates to a method for producing a double metal cyanide catalyst (DMC), comprising reacting an aqueous solution of a cyanide-free metal salt, an aqueous solution of a metal cyanide salt, an organic complexing ligand and a complex-forming component to form a dispersion, wherein the reaction is carried out using a mixing nozzle, and wherein the process temperature of the dispersion during the reaction is 26 to 49 ℃. Another subject of the invention is a double metal cyanide catalyst (DMC) obtainable according to the process of the invention and the use of said DMC catalyst for the preparation of polyoxyalkylene polyols.

Description

Process for preparing double metal cyanide catalysts
The present invention relates to an improved process for the preparation of Double Metal Cyanide (DMC) catalysts for the preparation of polyoxyalkylene polyols, preferably polyether polyols and/or polyether carbonate polyols. Another subject matter is the DMC catalysts obtainable by this process and the use of the catalysts according to the invention for preparing polyoxyalkylene polyols.
DMC catalysts are known in principle from the prior art (see, for example, U.S. Pat. No. 5,172,442, U.S. Pat. No. 5,241, and U.S. Pat. No. 5,182, and U.S. Pat. No. 62,62). DMC catalysts as described, for example, in U.S. Pat. No. 5,172,241, EP-A700 949, EP-A743 093, EP-A761 708, WO 97/40086, WO 98/16310 and WO 00/47649 are extremely active in the homopolymerization of epoxides and enable the preparation of polyether polyols at extremely low catalyst concentrations (25 ppm or less) so that it is generally no longer necessary to separate the catalyst from the finished product. Typical examples are the highly active DMC catalysts described in EP-A700 949, which contain not only double metal cyanide compounds, such as zinc hexacyanocobaltate (III), and organic complexing ligands, such as tert-butanol, but also polyethers having a number average molecular weight of greater than 500 g/mol.
WO 01/39883 A1 discloses a process for preparing Double Metal Cyanide (DMC) catalysts for preparing polyether polyols by polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms, in which process a mixing nozzle, preferably a jet disperser, is used to prepare the DMC catalyst dispersion. The DMC catalysts thus prepared have improved activity in the preparation of polyether polyols, reduced particle size and a narrower particle size distribution.
WO 01/80994 A1 likewise discloses a process for preparing Double Metal Cyanide (DMC) catalysts, in which an aqueous solution of a metal salt and a metal cyanide salt is first reacted in the presence of an organic complexing ligand and optionally one or more other complex-forming components to form a DMC catalyst dispersion, this dispersion is then filtered, the filter cake is subsequently washed by means of a filter cake, the filter cake is washed with an aqueous solution or a non-aqueous solution of the organic complexing ligand and optionally one or more other complex-forming components, and the washed filter cake is finally dried after optional extrusion or mechanical removal of water. The disclosed process shortens the catalyst preparation time, wherein the resulting catalyst has comparable activity in polyether polyol preparation as a reference catalyst.
WO 2011/144523 A1 discloses polyether carbonate polyols formed from one or more H-functional starter substances, one or more alkylene oxides and carbon dioxide in the presence of at least one double metal cyanide catalyst, wherein the cyanide-free metal salt, the metal cyanide salt or both mentioned salts used for the preparation of the double metal cyanide catalyst are reacted in the presence of a specific amount of a basic compound. These DMC catalysts provide improved selectivity to facilitate the formation of linear polyether carbonate polyols.
EP 700 949 A2 describes DMC catalysts which contain a DMC compound, an organic complexing ligand and 5% to 80% by weight of a polyether having a number average molecular weight of > 500 g/mol, wherein the preparation of the DMC catalyst dispersion is carried out at room temperature. The catalysts used are essentially active in the preparation of polyether polyols.
The relevance of temperature regulation/control in the preparation of DMC dispersions and their effect on DMC catalyst activity for the formation of polyoxyalkylene polyols is not disclosed in the prior art.
It is an object of the present application to provide an improved process for preparing Double Metal Cyanide (DMC) catalysts having a further increased catalytic activity in the preparation of polyoxyalkylene polyols, preferably polyether polyols and/or polyether carbonate polyols, wherein such improved activity leads to a reduction in the product viscosity in the catalyst test according to the "8K diol compression test" described, for example, in WO 98/16310 A1. The object was therefore to provide more catalytically active DMC catalysts which lead to polyoxyalkylene polyols, preferably polyether polyols and/or polyether carbonate polyols, having reduced viscosity, which facilitate the further processibility of the polyoxyalkylene polyols in subsequent urethanization reactions. The increased catalyst activity also enables a reduction in the catalyst usage, which improves the economic viability of the process.
At the same time, the DMC catalyst dispersion production process should be carried out with comparable simple device arrangements, low energy consumption during shearing, good temperature control and likewise good scalability in comparison with the known industrial processes, so that it can be implemented simply in existing DMC catalyst production processes, for example in loop reactions.
Surprisingly, it has now been found that the above object is achieved by a process for preparing double metal cyanide catalysts (DMC), which comprises
i) In a first step, reacting an aqueous solution of a cyanide-free metal salt, an aqueous solution of a metal cyanide salt, an organic complexing ligand, and a complex-forming component to form a dispersion;
wherein the reaction is carried out using a mixing nozzle;
and wherein the process temperature of the dispersion during the reaction is from 26 ℃ to 49 ℃.
Cyanide-free metal salts
Cyanide-free metal salts suitable for preparing double metal cyanide compounds preferably have the general formula (I)
M(X) n (I)
Wherein the method comprises the steps of
M is selected from metal cations Zn 2+ 、Fe 2+ 、Ni 2+ 、Mn 2+ 、Co 2+ 、Sr 2+ 、Sn 2+ 、Pb 2+ And Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the M is preferably Zn 2+ 、Fe 2 + 、Co 2+ Or Ni 2+ ，
X is one or more (i.e., different) anions, preferably an anion selected from the group consisting of halide (i.e., fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate, and nitrate;
when x=sulfate, carbonate or oxalate, n is 1, and
when x=halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate, n is 2,
or suitable cyanide-free metal salts of the general formula (II)
M r (X) 3 (II)
Wherein the method comprises the steps of
M is selected from metal cations Fe 3+ 、Al 3+ And Cr (V) 3+ ，
X is one or more (i.e., different) anions, preferably an anion selected from the group consisting of halide (i.e., fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate, and nitrate;
when x=sulfate, carbonate or oxalate, r is 2, and
when x=halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate or nitrate, r is 1,
or suitable cyanide-free metal salts have the general formula (III),
M(X) s (III)
wherein the method comprises the steps of
M is selected from metal cations Mo 4+ 、V 4+ And W is 4+ ，
X is one or more (i.e., different) anions, preferably an anion selected from the group consisting of halide (i.e., fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate, and nitrate;
when x=sulfate, carbonate or oxalate, s is 2, and
when x=halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate or nitrate, s is 4,
or suitable cyanide-free metal salts have the general formula (IV),
M(X) t (IV)
wherein the method comprises the steps of
M is selected from metal cations Mo 6+ And W is 6+ ，
X is one or more (i.e., different) anions, preferably an anion selected from the group consisting of halide (i.e., fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate, and nitrate;
when x=sulfate, carbonate or oxalate, t is 3, and
when x=halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate or nitrate, t is 6.
In a preferred embodiment of the method according to the invention, the cyanide-free metal salt of the aqueous solution of the cyanide-free metal salt is one or more compounds and is selected from the group consisting of zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, cobalt (II) thiocyanate, nickel (II) chloride and nickel (II) nitrate.
Metal cyanide salts
The metal cyanide salts suitable for preparing the double metal cyanide compounds preferably have the general formula (V)
(Y) a M'(CN) b (A) c (V)
Wherein the method comprises the steps of
M' is selected from one or more metal cations of Fe (II), fe (III), co (II), co (III), cr (II), cr (III), mn (II), mn (III), ir (III), ni (II), rh (III), ru (II), V (IV) and V (V); m' is preferably one or more metal cations selected from the group consisting of Co (II), co (III), fe (II), fe (III), cr (III), ir (III) and Ni (II),
y is selected from alkali metals (i.e. Li + 、Na + 、K + 、Rb + 、Cs + ) And alkaline earth metals (i.e. Be) 2+ 、Ca 2+ 、Mg 2+ 、Sr 2+ 、Ba 2+ ) Is selected from the group consisting of metal cations,
a is selected from one or more anions selected from halide (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate or nitrate, and
a. b and c are integers wherein the values of a, b and c are selected to ensure the electroneutrality of the metal cyanide salt; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has a value of 0.
In a preferred embodiment of the process according to the invention, the metal cyanide salt of the aqueous solution of the metal cyanide salt is one or more compounds and is selected from the group consisting of potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyanocobaltate (III).
The preferred double metal cyanide compounds contained in the DMC catalysts according to the invention are compounds of the formula (VI)
M x [M' x ,(CN) y ] z (VI),
Wherein M is as defined in formulae (I) to (IV) and
m' is as defined in formula (V) and
x, x', y and z are integers and are selected to ensure the electroneutrality of the double metal cyanide compound.
Preferably, the method comprises the steps of,
x=3, x' =1, y=6 and z=2,
m=zn (II), fe (II), co (II) or Ni (II) and
m' =co (III), fe (III), cr (III), or Ir (III).
In a preferred embodiment of the process according to the invention, the double metal cyanide compound is one or more compounds and is selected from the group consisting of zinc hexacyanocobaltate (III), zinc hexacyanoiridium (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III). Zinc hexacyanocobaltate (III) is particularly preferably used.
Organic complexing ligands
Organic complexing ligands which are added in the preparation of DMC catalysts are disclosed, for example, in U.S. Pat. No. 5,6778 (see especially column 6, lines 9 to 65), U.S. Pat. No. 4,096, U.S. Pat. No. 3,972,67, EP-A700 949, EP-A761 708, JP 4 145 123, U.S. Pat. No. 6, 5 470 813, EP-A743 093 and WO-A97/40086. For example, the organic complexing ligands used are water-soluble organic compounds having heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with double metal cyanide compounds. Preferred organic complexing ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof. Particularly preferred organic complexing ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), compounds containing aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (such as ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol monomethyl ether and 3-methyl-3-oxetane methanol). Most preferred organic complexing ligands are selected from one or more of dimethoxyethane, t-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butin-2-ol, ethylene glycol mono-t-butyl ether and 3-methyl-3-oxetane methanol.
In a preferred embodiment of the process according to the invention, the organic complexing ligand is one or more compounds and is selected from the group consisting of dimethoxyethane, t-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-t-butyl ether and 3-methyl-3-oxetane methanol.
Complex-forming components
In the process for preparing DMC catalysts according to the invention, one or more complex-forming components from the group of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamides, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid-co-maleic acid), polyacrylonitrile, polyalkylacrylates, polyalkylmethacrylates, polyvinylmethyl ethers, polyvinylethyl ethers, polyvinyl acetates, polyvinyl alcohols, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinylmethyl ketones, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid copolymers and maleic anhydride copolymers, hydroxyethylcellulose and polyacetals, or glycidyl ethers, glycosides, carboxylic esters, esters or amides of polyols, cyclodextrins or phosphorus compounds are used.
In the process according to the invention for preparing DMC catalysts, polyethers are preferably used as component for forming the complex.
In a preferred embodiment, the polyethers have a number average molecular weight of > 500 g/mol, wherein the number average molecular weight is calculated from the OH number determined.
The OH number was determined according to DIN 53240.
Suitable polyethers include those prepared by ring opening polymerization of cyclic ethers, which for example also contain oxetane polymers as well as tetrahydrofuran polymers. Various catalysis is possible for this. The polyethers here have suitable end groups, for example hydroxyl, amine, ester or ether end groups.
In a particularly preferred embodiment, the polyethers have an average hydroxyl functionality of from 2 to 8 and a number average molecular weight of from 500 g/mol to 10000 g/mol, preferably from 700 g/mol to 5000 g/mol, the number average molecular weight being calculated from the OH number determined.
In a particularly preferred embodiment, the polyether is a polyether polyol, wherein the polyether polyol is obtained by reaction of an alkylene oxide and an H-functional starter compound in the presence of an acidic, basic and/or organometallic catalyst. These organometallic catalysts are, for example, double Metal Cyanide (DMC) catalysts.
Suitable polyether polyols are poly (oxypropylene) polyols, poly (oxypropylene) oxyethylene polyols, polytetramethylene ether glycols and block copolymers containing poly (oxy) ethylene, poly (oxy) propylene and/or poly (oxy) butylene blocks, for example poly (oxy) ethylene-poly (oxy) propylene block copolymers having terminal poly (oxy) ethylene blocks.
In a preferred embodiment, the polyether polyol is a poly (oxypropylene) polyol having a number average molecular weight of > 500 g/mol, wherein the number average molecular weight is calculated from the measured OH number.
In a particularly preferred embodiment, the polyether polyol is a poly (oxypropylene) polyol, preferably a poly (oxypropylene) diol and/or a poly (oxypropylene) triol, having a number average molecular weight of 700 g to 4000 g/mol, wherein the number average molecular weight is calculated from the measured OH number.
In an alternative embodiment, the polyether has an average hydroxyl functionality of from 2 to 8 and a number average molecular weight of from 150 g/mol to less than 500 g/mol, preferably from 200 g/mol to 400 g/mol, wherein the number average molecular weight is calculated from the measured OH number.
In a preferred alternative embodiment, the alternative polyethers are polyether polyols, wherein these alternative polyether polyols have an average hydroxyl functionality of from 2 to 8 and a number average molecular weight of from 150 g/mol to less than 500 g/mol, preferably an average hydroxyl functionality of from 2 to 8 and a number average molecular weight of from 200 g/mol to 400 g/mol, wherein the number average molecular weight is calculated from the measured OH number. These alternative polyether polyols are likewise obtained by the reaction of alkylene oxides with H-functional starter compounds in the presence of acidic, basic and/or organometallic catalysts. These organometallic catalysts are, for example, double Metal Cyanide (DMC) catalysts.
Suitable alternative polyether polyols are poly (oxypropylene) polyols, poly (oxypropylene) oxyethylene polyols, polytetramethylene ether glycols and block copolymers containing poly (oxy) ethylene, poly (oxy) propylene and/or poly (oxy) butylene blocks, for example poly (oxy) ethylene-poly (oxy) propylene block copolymers having terminal poly (oxy) ethylene blocks. Tripropylene glycol, triethylene glycol, tetrapropylene glycol, tetraethylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and mono-and dialkyl ethers of glycols and poly (alkylene glycols) are also suitable.
In a particularly preferred alternative embodiment, the alternative polyether polyols are polypropylene glycols and/or polyethylene glycols having a number average molecular weight of from 150 g/mol to less than 500 g/mol, the number average molecular weight being calculated from the measured OH number.
Mixing nozzle
DMC catalyst dispersions are prepared using mixing nozzles (e.g.smooth-jet nozzles, levos nozzles, bosch nozzles, etc.), preferably jet dispersers as described in German patent application WO 01/39883 A1.
The basic structure and mode of operation of a suitable mixing nozzle will be described below. Fig. 1 shows a schematic structure of a simple smooth jet nozzle. Reactant stream 1 is first accelerated in nozzle 3 and injected at a high flow rate into slow flowing reactant stream 2. Here, reactant stream 2 accelerates and reactant stream 1 decelerates. A part of the kinetic energy of the reactant jet 1 is converted into heat in this process and is therefore no longer available for the mixing operation. The two reactant streams are then mixed by turbulent break-up of the resulting jet into vortices of different sizes (vortex cascade). In this way, the concentration difference can be reduced significantly more rapidly than in stirred tanks, since a significantly greater and more uniform power density can be achieved. The average power density P is calculated here by the following formula:
wherein Δp is the pressure loss in the nozzle
Volume flow rate
V: the volume of the nozzle hole.
The use of such a nozzle shall be referred to hereinafter as method 1.
In a smooth jet nozzle, the first reactant stream is first accelerated in the nozzle and injected at a high flow rate into the slowly flowing second reactant stream. The two reactant streams are then mixed by turbulent break-up of the resulting jet into vortices of different sizes (vortex cascade). In this way, the concentration difference can be reduced significantly more rapidly than in stirred tanks, since a significantly greater and more uniform power density can be achieved.
Jet disperser
For the method according to the invention, it is preferred to use a jet disperser as shown in fig. 2 or fig. 3. The jet disperser (fig. 2) may be constructed such that two nozzles 5 and 6 are arranged in succession. The reactant stream 1 is first greatly accelerated in the nozzle 5 by a cross-sectional constriction. The accelerated jet is sucked into the second component here due to the high flow velocity. The nozzle spacing is preferably chosen such that only nucleation occurs in the mixing chamber 4, without crystal growth, due to the short residence time. The decisive factor for the optimal design of the jet disperser is thus the nucleation speed of the solids. The residence time is advantageously adjusted to 0.0001 s to 0.15 s, preferably 0.001 s to 0.1 s. Crystal growth occurs at the earliest in outlet 3. The diameter of the nozzle 6 should preferably be chosen such that the partially mixed reactant stream is further accelerated therein. Due to the shear forces thus additionally generated in the nozzle 6, a homogeneous mixing state is achieved in a shorter time due to a faster vortex breakdown than in the method 1. Thus, even at very high nucleation rates compared to method 1Ideal mixing of the reactants can also be achieved in the case of a moderate precipitation reaction, so that a specific stoichiometric composition can be adjusted during the precipitation reaction. Pressure loss in nozzle of 0.1 bar to 1000 bar or 1 x 10 7 W/m 3 To 1 x 10 13 W/m 3 Nozzle diameters of 5000 μm to 50 μm, preferably 2000 μm to 200 μm, have proven advantageous. This mixing operation shall be referred to hereinafter as method 2.
Depending on the desired particle size, a further n nozzles (where n=1-5) may be connected downstream to obtain a multistage jet disperser. Fig. 3 shows such a multistage jet disperser. After nozzle 6, the dispersion is again led through nozzle 7. The same applies to the design of the nozzle diameter for the nozzle 6.
An additional advantage of the additional disperser compared to method 2 is that the formed particles can be mechanically crushed by large shear forces in the nozzle. Particles having a diameter of 10 μm to 0.1 μm can thereby be produced. Instead of a plurality of nozzles in series, the comminution can also be effected by circulation of the dispersion. The use of such a nozzle is hereinafter labeled method 3.
Heating of the dispersion can be caused by energy dissipation in the nozzle and by crystallization enthalpy. Since temperature can have a significant impact on the crystal formation process, a heat transfer tool can be installed downstream of the mixing element for isothermal process mode.
The problem-free scaling can be achieved, for example, by using a larger number of holes, connecting a plurality of mixing elements in parallel or enlarging the free nozzle area. However, enlarging the free nozzle area cannot be achieved by increasing the nozzle diameter, because there is a possibility that core flow (Kernstrom) will occur as a result of this, so that the mixing result will be poor. For nozzles with a large free nozzle area, it is therefore preferred to use slits with a corresponding area.
The DMC catalyst dispersion is prepared according to the present invention using a mixing nozzle, preferably a jet disperser. Examples of suitable devices are shown in fig. 4 and 5. Fig. 4 shows a semi-batch process using a loop reactor and fig. 5 shows a continuous process for preparing a DMC catalyst dispersion.
In one embodiment of the process according to the invention, the preparation of the double metal cyanide catalyst (DMC) comprises
i) In a first step, reacting an aqueous solution of a cyanide-free metal salt, an aqueous solution of a metal cyanide salt, an organic complexing ligand, and a complex-forming component to form a dispersion;
wherein the reaction is carried out using a mixing nozzle;
and wherein the temperature of the dispersion during the reaction is from 26 ℃ to 49 ℃;
(ii) Optionally, in a second step, separating solids from the dispersion obtained from (i);
(iii) Optionally, in a third step, the separated solid is washed with an aqueous solution of an organic complexing ligand by means of cake washing;
(iv) And optionally, in a fourth step, drying the resulting solid.
Step i)
The cyanide-free metal salts used in stoichiometric excess (at least 50 mol%, based on the metal cyanide salt), for example aqueous solutions of zinc chloride, and aqueous solutions of metal cyanide salts, for example potassium hexacyanocobaltate, are reacted here preferably first in the presence of an organic complexing ligand, which may be, for example, tert-butanol, to form a dispersion. According to the invention, such DMC catalyst dispersions are prepared using a mixing nozzle, preferably a jet disperser.
The preparation of DMC catalyst dispersions in a semi-batch process using a jet disperser in combination with a loop reactor (according to FIG. 4) is described below. Here, the aqueous solution of the cyanide-free metal salt can be circulated from the vessel B2 and the aqueous solution of the metal cyanide can be metered in from the vessel B1 or vice versa. When the two streams are combined in the mixing element M, a dispersion of the DMC compound is formed. Dispersions of DMC compounds can be prepared by methods 1, 2 or 3, preferably by methods 2 or 3. The advantage of these methods is the possibility to achieve a constant reactant ratio throughout the precipitation process.
Preferably, the dispersion formed after precipitation is circulated through the jet disperser for additional minutes to hours.
The nozzle diameter is preferably 2000 μm to 200 μm, the pressure loss in the nozzle being 0.1 bar to 1000 bar.
The organic complexing ligand can be present here in the aqueous solution of the cyanide-free metal salt and/or in the aqueous solution of the metal cyanide salt or it can be metered directly into the dispersion obtained after precipitation of the double metal cyanide compound (via vessel B1 or B2).
Preferably, the complex-forming components are subsequently also metered into the dispersion circulated through the jet disperser via vessel B1 or B2. The components forming the complex are preferably used here in a mixture of water and organic complexing ligands.
The metering of the complex-forming components into the cycle and the subsequent recirculation is preferably carried out at a pressure loss in the nozzle of 0.001 bar to 10 bar.
The DMC catalyst dispersion can also be prepared in a continuous process as shown by way of example in FIG. 5 according to the present invention. The aqueous solution of the cyanide-free metal salt and the aqueous solution of the metal cyanide salt are reacted according to method 1, 2 or 3 in a mixing element M1 to form a dispersion. The organic complexing ligand may be present in the aqueous solution of the cyanide-free metal salt and/or in the aqueous solution of the metal cyanide salt. In this case, the mixing stage M2 in fig. 5 is omitted. The organic complexing ligand may also be added via the mixing element M2 after precipitation of the double metal cyanide compound. In order to increase the residence time of the dispersion, the dispersion can be circulated via the mixing element M2. The components forming the complex, preferably in a mixture of water and organic complexing ligand, may then be added to the mixing element M3 and recycled to increase the residence time.
Process temperature
In a preferred embodiment of the process according to the invention, the temperature in step i) is from 28℃to 47 ℃, preferably from 29℃to 42 ℃, particularly preferably from 30℃to 40 ℃. Here, the process temperature corresponds to the process temperature in the container B2 in fig. 4. The process temperatures of 29 ℃ to 42 ℃ and 30 ℃ to 40 ℃ result in further improvements in the activity of the DMC catalyst.
Step (ii)
In a preferred embodiment of the process according to the invention, in a second step (ii) solids are separated from the dispersion obtained from (i).
The solids (i.e. the precursors of the catalysts according to the invention) are separated from the dispersion here by known techniques, such as centrifugation or filtration.
Suitable filter arrangements are described, for example, in "Ullmann's Encyclopedia of Industrial Chemistry", volume B2, chapters 9 and 10, VCH, weinheim, 1988 and H. Gasper, D. Oechsle, E. Pongatz (eds.) "Handbuch der industriellen Fest/Flussig-Filtration", wiley-VCH Verlag GmbH, weinheim, 2000.
The pressure gradient required for filtration can be applied here by gravity, by centrifugal force (e.g. a filter centrifuge), preferably by a gas pressure difference (e.g. a vacuum filter or a pressure filter) or by liquid pressure (e.g. a filter press, a rotary drum filter or a disc filter and possibly a cross-flow filtration module).
For separating off the catalyst, either discontinuously operated or continuously operated filter devices can be used. Examples of discontinuously operating filter devices are knife filter centrifuges (Sch ä l filter basket) and bag filter centrifuges (Stulpfilter basket), membrane, chamber, frame or tube filter presses, automatic extrusion devices, platen, cartridge and plate filters and vacuum and pressure suction filters. Examples of continuously operating filtration devices are belt presses, pressure and vacuum drum filters, pressure and vacuum disc filters, belt filters and cross-flow filters.
For filtering the DMC catalyst dispersion, particularly suitable on a laboratory scale are vacuum or pressure filters or vacuum or pressure suction filters; particularly suitable at pilot and production scales are pressure suction filters, filter presses and automatic filter presses.
Membrane presses have proven particularly suitable at both pilot and pilot scale. It enables the DMC catalyst dispersion to be filtered by means of a suitable filter cloth, preferably a membrane cloth, and as a result of an applied liquid pressure gradient.
The filtration is carried out in particular at a temperature of from 10 to 80 ℃. The pressure difference applied may be from 0.001 bar to 200 bar, preferably from 0.1 bar to 100 bar, particularly preferably from 0.1 bar to 25 bar, depending on the device used.
Step (iii)
The isolated solid obtained in step (ii) may be washed by means of redispersion or cake washing.
In a preferred embodiment of the process according to the invention, in the third step (iii), the isolated solid is washed with an aqueous solution of the organic complexing ligand by means of cake washing.
The cake washing is preferably carried out here by pulping or preferably by flow-through washing. Here, the washing liquid flows through the filter cake and displaces the liquid previously contained in the filter cake, wherein the diffusion effect also becomes effective. Removal of water from the washed filter cake may be achieved by gas pressure differential, centrifugal force or mechanical pressing, or preferably in combination (removal of water by gas pressure differential and subsequent mechanical pressing). The pressure for mechanical pressing can be applied here both mechanically and via the membrane.
The preparation process is simplified and thus also accelerated by means of cake washing. The preferred ratio of wash liquor to cake volume is an amount such that complete exchange of the amount of liquid present in the original cake is achieved.
In an alternative preferred embodiment variant of the method according to the invention, the isolated solid is subsequently washed in a third process step with an aqueous solution of the organic complexing ligand (for example by redispersion and subsequent re-separation by filtration or centrifugation). Whereby, for example, water-soluble byproducts, such as potassium chloride, can be removed from the catalyst according to the invention. The amount of organic complexing ligand in the aqueous wash solution is preferably from 40 to 80 wt% based on the total solution.
Optionally, in a third step, the complex-forming component is added to the aqueous wash liquor, preferably in an amount of 0.5 to 5% by weight, based on the total solution.
It is also advantageous to wash the separated solids more than once. Preferably, in the first washing step (iii-1) an aqueous solution of the organic complexing ligand is used (e.g. by redispersion and subsequent re-separation by filtration or centrifugation) to thereby remove e.g. water soluble by-products such as potassium chloride from the catalyst according to the invention. It is particularly preferred that the amount of organic complexing ligand in the aqueous wash liquor is from 40 to 80 wt.%, based on the total solution of the first wash step. In the further washing step (iii-2), the first washing step is repeated one or more times, preferably 1 to 3 times, or a non-aqueous solution, for example, a mixture or solution of the organic complexing ligand and the complex-forming component (preferably 0.5 to 5% by weight based on the total amount of the washing liquid of step (iii-2)) is preferably used as the washing liquid, and the solid is washed one or more times, preferably 1 to 3 times.
Step (iv)
In a preferred embodiment of the process according to the invention, in the fourth step (iv), the resulting solid is subsequently dried.
The separated and optionally washed solid is herein, optionally after comminution, subsequently dried at a temperature of typically 20-100 ℃ and a pressure of typically 0.1 mbar to standard pressure (1013 mbar).
Steps (ii) and (iii)
In a preferred embodiment of the method according to the invention, steps (ii) and (iii) are carried out in a filter press.
It has proven advantageous to squeeze the washed filter cake after washing at a pressure of 0.5 to 200 bar, preferably at as high a pressure as possible. This can be done, for example, directly after washing the filter cake in a filter press or by means of other suitable pressing devices which are able to apply mechanical pressure so that the liquid present in the filter cake can escape through a membrane or a suitable filter cloth. Mechanical removal of water from the filter cake, which is carried out after washing of the filter cake and preferably before drying, may preferably be carried out in a filter press, preferably by mechanical pressing by means of pressure applied to the membrane. Mechanical removal of water preferably results in as substantial removal of wash liquor from the filter cake as possible.
Steps (ii), (iii) and (iv)
The DMC catalyst is then dried at a temperature of about 20 to 100℃and a pressure of about 0.1 mbar to standard pressure (1013 mbar). Contact and convection dryers and spray dryers are suitable for this. The drying is preferably also carried out directly in the apparatus for mechanical removal of the liquid, when these apparatuses are suitable for this (for example suction dryers, centrifugal dryers, "hot-press filters").
In a particularly preferred embodiment of the process according to the invention, steps (ii), (iii) and (iv) are carried out in a heatable filter press.
The method preferably uses a heatable filter press. This is constructed as a conventional filter press with a membrane stack (membrane pack). The membrane plate used differs from conventional templates in terms of construction in that the heating medium can flow through the space behind the membrane. Preferably, a liquid-tight (so-called "drip-proof" or "gas-tight") membrane filter plate is used.
The heated heating medium flows through the filter cake at the rear side of the filter press membrane (which is completely separated from the filter cake by the filter press membrane and the filter medium) and heats the filter cake in the process. The pressurized medium is here at a sufficiently high pressure to ensure that the membrane is in contact with the filter cake. The filter cake may be heated on one or both sides. In view of the drying time, heating on both sides is advantageous.
Vacuum was applied to the filtrate side to aid in the drying process. Such a vacuum may be generated, for example, by a liquid ring pump. The vapor stream that is drawn off is cooled upstream of a vacuum pump to condense out volatile components (e.g., t-butanol and water). The measurement parameters and control parameters are the amount of coagulation, the pressure in the filtrate system of the press and the filter cake temperature.
In the process, the membrane pressurization pressure is preferably from 0.1 bar to 10 bar. The temperature of the pressurizing and heating medium is 30 to 80 ℃, preferably 40 to 60 ℃. The pressure on the filtrate side is preferably less than 100 mbar. The flow rate of the heating medium should be chosen to be sufficiently high to achieve good heat transfer between the heating medium and the product. The drying time is usually from several minutes to several hours, usually from 1 to 10 hours. A residual moisture content below a target value of about 5% is reliably achieved with this type of drying.
In a further process step, the product from which the minor components are separated and removed can be ground and packaged.
Product claims defined by the method
Another subject of the invention is DMC catalysts prepared by the process according to the invention.
A further subject matter of the invention is the use of DMC catalysts prepared by the process according to the invention for preparing polyoxyalkylene polyols, preferably polyether polyols by polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms, and/or polyether carbonate polyols by polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms in the presence of carbon dioxide.
The DMC catalysts prepared by the process according to the invention can generally be used in very low concentrations (25 ppm and below, based on the amount of polyoxyalkylene polyol, preferably polyether polyol, to be prepared) due to their very high activity. If polyoxyalkylene polyols, preferably polyether polyols, prepared in the presence of DMC catalysts prepared by the process according to the present invention are used to prepare polyurethanes, the removal of catalyst from the polyoxyalkylene polyols, preferably polyether polyols, can be omitted without adversely affecting the product quality of the resulting polyurethanes.
Examples
The OH number was determined according to DIN 53240. The viscosity was determined by means of a rotational viscometer (Physica MCR 51, manufacturer: anton Paar) according to DIN 53018.
Preparation of DMC catalyst:
example 1 (comparative):
the catalyst was prepared using the apparatus according to FIG. 4 of WO 01/39883 A1.
In a loop reactor containing a jet disperser with holes (diameter 0.7 mm) according to fig. 2 of WO 01/39883 A1, a solution of 258 g zinc chloride in 937 g distilled water and 135 g t-butanol was circulated at 25 deg.c (measured in vessel D2 in fig. 4 of WO 01/39883 A1). A solution of 26 g of potassium hexacyanocobaltate in 332 g of distilled water was metered in. The pressure loss in the jet disperser is here 2.9 bar. Subsequently, the dispersion formed was circulated for 60 minutes at 25℃and a pressure loss in a jet disperser of 2.9 bar. Thereafter, a mixture of 5.7 g of tert-butanol, 159 g of distilled water and 27.6 g of polypropylene glycol 1000 (PPG-1000) was metered in, and the dispersion was then circulated at 25℃and a pressure loss in a jet disperser of 2.9 bar for 80 minutes.
At 20 cm 3 230 grams of the resulting dispersion was filtered through a pressure suction filter of filter area followed by washing with a mixture of 82 grams t-butanol, 42.3 grams distilled water and 1.7 grams polypropylene glycol 1000. The washed cake was mechanically pressed between two filter papers and finally dried at 60 ℃ under a high vacuum of about 0.05 bar (absolute) for 2 hours.
Example 2:
example 2 was performed similarly to example 1 (comparative) except that the DMC dispersion was prepared at 30℃instead of 25 ℃.
Example 3:
example 3 was performed similarly to example 1 (comparative) except that the DMC dispersion was prepared at 35℃instead of 25 ℃.
Example 4:
example 4 was performed similarly to example 1 (comparative) except that the DMC dispersion was prepared at 40℃instead of 25 ℃.
Example 5 (comparative):
example 5 (comparative) was performed similarly to example 1 (comparative) except that the DMC dispersion was prepared at 50℃instead of 25 ℃.
Example 6 (comparative):
example 6 (comparative) was conducted similarly to example 1 (comparative) except that the DMC dispersion was prepared at 70℃instead of 25 ℃.
Example 7 (comparative):
the catalyst was prepared using the apparatus according to FIG. 4 of WO 01/39883 A1.
In a loop reactor containing a jet disperser with holes (diameter 0.7 mm) according to fig. 2 of WO 01/39883 A1, a solution of 258 g zinc chloride in 937 g distilled water and 135 g t-butanol was circulated at 25 ℃. A solution of 26 g of potassium hexacyanocobaltate in 332 g of distilled water was metered in. The pressure loss in the jet disperser is here 5.0 bar. Subsequently, the dispersion formed was circulated for 60 minutes at 25℃and a pressure loss in a jet disperser of 5.0 bar. Thereafter, a mixture of 5.7 g of t-butanol, 159 g of distilled water and 27.6 g of polypropylene glycol 1000 was metered in, and the dispersion was then circulated for 80 minutes at 25℃and a pressure loss in a jet disperser of 5.0 bar.
At 20 cm 3 230 grams of the resulting dispersion was filtered through a pressure suction filter of filter area followed by washing with a mixture of 82 grams t-butanol, 42.3 grams distilled water and 1.7 grams polypropylene glycol 1000. The washed cake was mechanically pressed between two filter papers and finally dried at 60 ℃ under a high vacuum of about 0.05 bar (absolute) for 2 hours.
Example 8:
example 8 was performed similarly to example 7 (comparative) except that the DMC dispersion was prepared at 30℃instead of 25 ℃.
Example 9:
example 9 was performed similarly to example 7 (comparative) except that the DMC dispersion was prepared at 35℃instead of 25 ℃.
Example 10:
example 10 was performed similarly to example 7 (comparative) except that the DMC dispersion was prepared at 40℃instead of 25 ℃.
Example 11 (comparative):
example 11 (comparative) was conducted similarly to example 7 (comparative) except that the DMC dispersion was prepared at 50℃instead of 25 ℃.
Example 12 (comparative):
example 12 (comparative) was conducted similarly to example 7 (comparative) except that the DMC dispersion was prepared at 70℃instead of 25 ℃.
Example 13 (comparative):
example 13 (comparative) was carried out analogously to example 3, except that for the preparation of the DMC catalyst the component polypropylene glycol 1000 forming the complex was replaced by sodium cholate.
Catalyst test ("8K glycol compression test"):
the DMC catalyst is tested in the so-called "8K diol compression test". Here, starting from a difunctional polypropylene glycol starter ("Arcol Polyol 725" from Covestro company) with an OH number=147 mg KOH/g, polypropylene glycols ("8K glycols") with a calculated OH number=14 mg KOH/g, i.e. a molecular weight=8000 g/mol, were prepared at a short propylene oxide metering time (30 minutes). The decisive evaluation criterion for the catalyst quality/activity in this test is the viscosity of the resulting polyol, with DMC catalysts having increased quality/activity leading to lower 8K diol viscosities.
The general implementation is as follows:
a1 liter stainless steel reactor was initially charged with 75 grams of difunctional polypropylene glycol starter (OH number=147 mg KOH/g) and 30.7 milligrams of DMC catalyst. After 5 shifts between nitrogen and a vacuum of 0.1 to 3.0 bar (absolute), the reactor contents were heated to 130 ℃ with stirring (800 revolutions per minute). The mixture is then stripped with nitrogen at 130℃and 100 mbar (absolute) for 30 minutes. 7.5 g of propylene oxide were then added at 130℃and 100 mbar (absolute) to activate the catalyst. Catalyst activation is manifested as an accelerated pressure drop in the reactor. After the catalyst had been activated, the remaining propylene oxide (685.7 g) was metered in over 30 minutes at 130℃with stirring (800 revolutions per minute). After a post-reaction time of 30 minutes at 130 ℃, the volatile constituents are distilled off in vacuo (< 10 mbar) at 90 ℃ for 30 minutes. The product was then cooled to room temperature and removed from the reactor.
The OH number and viscosity (25 ℃) of the resulting product were measured. In the case of a measured OH value deviating from the calculated OH value (14 mg KOH/g), the "corrected viscosity" is determined from the measured viscosity using the following formula:
corrected viscosity (25 ℃) =measured viscosity (25 ℃) + 659 x (OH number-14)
The results of the catalyst test in the "8K glycol compression test" are summarized in table 1.
Table 1:
catalyst test/example DMC catalyst/example Pressure at jet disperser [ p ]] Temperature [ DEGC] OH number [ mg KOH/g ]] Viscosity 25 ℃/measurement [ mPas ]] Viscosity 25 ℃/correction [ mPas ]]
14 (comparison) 1 (comparison) 2.9 25 13.6 4595 4331
15 2 2.9 30 13.8 4125 3993
16 3 2.9 35 13.8 4305 4173
17 4 2.9 40 13.8 4310 4178
18 (comparison) 5 (comparison) 2.9 50 13.8 4525 4393
19 (comparison) 6 (comparison) 2.9 70 13.8 5305 5173
20 (comparison) 7 (comparison) 5.0 25 13.9 4500 4434
21 8 5.0 30 13.9 4190 4124
22 9 5.0 35 13.9 4120 4054
23 10 5.0 40 13.7 4495 4297
24 (comparison) 11 (comparison) 5.0 50 13.7 4610 4412
25 (comparison) 12 (comparison) 5.0 70 13.7 5385 5187
26 (comparison) 13 (comparative) x 2.9 35 13.9 5895 5829
* Sodium cholate replaces polypropylene glycol 1000 as a component forming the complex.
The results show that the lowest viscosity values (corrections) in the "8K diol compression test" are obtained at both pressure losses in the jet disperser of 2.9 bar and 5.0 bar when the temperature during the preparation of the DMC dispersion is 30-40 ℃.
It was also shown that a significantly higher viscosity (correction) is obtained if the complex-forming component polypropylene glycol 1000 is replaced by sodium cholate in the preparation of the DMC catalyst.

Claims (19)

1. A process for preparing a double metal cyanide catalyst DMC comprising
i) In a first step, reacting an aqueous solution of a cyanide-free metal salt, an aqueous solution of a metal cyanide salt, an organic complexing ligand, and a complex-forming component to form a dispersion, wherein the complex-forming component is a polyether;
wherein the reaction is carried out using a mixing nozzle;
and wherein the process temperature of the dispersion during the reaction is from 26 ℃ to 49 ℃, wherein the polyether is a polyether polyol.
2. The method as recited in claim 1, wherein the mixing nozzle is a jet disperser.
3. A method as claimed in claim 2, wherein the pressure loss in the jet disperser is 0.1 to 100 bar.
4. A method as claimed in claim 3, wherein the pressure loss in the jet disperser is 1 to 50 bar.
5. A method as claimed in claim 3, wherein the pressure loss in the jet disperser is 2 to 30 bar.
6. The process as claimed in claim 1, wherein the polyether has a number average molecular weight of ≡500 g/mol, wherein the number average molecular weight is calculated from the measured OH number.
7. The process as claimed in claim 1, wherein the polyether polyol is a poly (oxypropylene) polyol having a number average molecular weight of ≡500 g/mol, wherein the number average molecular weight is calculated from the measured OH number.
8. The method as set forth in claim 7 wherein the poly (oxypropylene) polyol is a poly (oxypropylene) diol and/or poly (oxypropylene) triol having a number average molecular weight of 700 g to 4000 g/mol, wherein the number average molecular weight is calculated from the measured OH number.
9. A process as claimed in any one of claims 1 to 8, wherein the process temperature in step i) is from 28 ℃ to 47 ℃.
10. The process of claim 9, wherein the process temperature in step i) is 29 ℃ to 42 ℃.
11. The process of claim 9, wherein the process temperature in step i) is from 30 ℃ to 40 ℃.
12. A method as claimed in any one of claims 1 to 8, wherein
(ii) In a second step, solids are separated from the dispersion obtained from (i).
13. A method as claimed in any one of claims 1 to 8, wherein
(iii) In a third step, the separated solid is washed with an aqueous solution of the organic complexing ligand by means of cake washing.
14. A method as claimed in any one of claims 1 to 8, wherein
(iv) In a fourth step, the resulting solid is dried.
15. A process as claimed in claim 12, wherein steps (ii) and (iii) are carried out in a filter press.
16. A process as claimed in claim 12 wherein steps (ii), (iii) and (iv) are carried out in a heatable filter press.
17. Double metal cyanide catalyst DMC obtainable by a process according to any of claims 1 to 8.
18. Use of a double metal cyanide catalyst DMC as claimed in any of claims 1 to 8 for the preparation of polyoxyalkylene polyols.
19. Use according to claim 18, wherein the polyoxyalkylene polyol is a polyether polyol and/or a polyether carbonate polyol.
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